Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G67/00—Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
  • C08G67/02—Copolymers of carbon monoxide and aliphatic unsaturated compounds

Definitions

• the invention relates to a process for the preparation of polymers of carbon monoxide with one or more alpha-olefins and with one or more other mono-­olefinically unsaturated compounds.
• High molecular weight linear alternating copolymers of carbon monoxide and ethylene can be prepared under the application of catalyst compositions on the basis of
• an oxycarbonyl moiety is present and in which the double bond is terminal.
• linear polymers can be prepared which are built up of units with the formula -(CO)-D′- and units with the formula -(CO)-E′-, which polymers contain on average fewer than 1000 -(CO)-D′- units per -(CO)-E′- unit, provided that in the catalyst compositions described hereinbefore having an anion of an acid with a pKa of less than 4 as component b), the diphosphine used as component c) is replaced by a nitrogen containing compound with the general formula in which X and Y represent the same or different organic bridging groups which each contain three or four atoms in the bridge, of which at least two are carbon atoms.
• the present patent application therefore relates to a process for the preparation of polymers of carbon monoxide with one or more alpha-olefins and with one or more other mono-olefinically unsaturated compounds in which linear polymers built up of units with the formula -(CO)-D′- and units with the formula -(CO)-E′- in which D′ and E′ represent monomer units originating from monomers D and E respectively and which polymers contain on average fewer than 1000 -(CO)-D′- units per -(CO)-E′- unit are prepared by polymerizing a mixture of carbon monoxide with one or more alpha-olefins (D) and with one or more mono-olefinically unsaturated compounds (E) in which compounds the double bond does not occur terminally and which compounds are selected from mono-olefins and compounds containing one or two carboxylate groups in the presence of a catalyst composition on the basis of:
• the patent application also relates to new polymers of carbon monoxide with one or more alpha-olefins and with one or more other mono-olefinically unsaturated compounds defined as follows:
• polymers are prepared which contain on average fewer than 750 and in particular fewer than 500 -(CO)-D′- units per -(CO)-E′- unit.
• the D and E monomers used in the process according to the invention preferably contain a maximum of 10 carbon atoms per molecule.
• Another preferred process uses as starting materials a monomer mixture containing just one D monomer and just one E monomer.
• suitable alpha-olefins for application as monomer D in the process according to the invention are ethylene, propylene and butene-1. Preference is given to ethylene.
• Suitable mono-olefins for application as monomer E in the process according to the invention, are butene-2, pentene-2, hexene-2, octene-2, 2,7-dimethyloctene-4, cyclopentene and cyclohexene. If a mono-olefin is used as monomer E, butene-2 is preferred.
• suitable compounds containing one or two carboxylate groups and which are suitable for use as monomer E in the process according to the invention are unsaturated monocarboxylic acids such as crotonic acid, alkyl esters of unsaturated monocarboxylic acids such as methyl crotonate and methyl pentene-3-oate, unsaturated dicarboxylic acids such as maleic acid and fumaric acid, monoalkyl esters of unsaturated dicarboxylic acids such as monomethyl maleate and monomethyl fumarate, dialkyl esters of unsaturated dicarboxylic acids such as dimethyl maleate, dimethyl fumarate and dimethyl hexene-3-dioate, anhydrides of unsaturated dicarboxylic acids such as maleic acid anhydride and lactones of unsaturated hydroxymonocarboxylic acids such as the lactone of ⁇ -hydroxycrotonic acid.
• unsaturated monocarboxylic acids such as crotonic acid
• a compound containing one or two carboxylate groups is used as monomer E, maleic acid anhydride is preferred.
• an E monomer containing one or two carboxylate groups polymers are obtained which contain as functional groups, besides carbonyl groups, carboxylate groups. These carboxylate groups may, just as the carbonyl groups, be at least partly converted by chemical modification into other functional groups. For example, carboxylic acid ester groups which can occur in the polymers may be converted by saponification into carboxylic acid groups.
• the polymer preparation according to the invention takes place under the application of a catalyst composition on the basis of
• the palladium compound used in the catalyst compositions as component a) is preferably a palladium salt of a carboxylic acid and in particular palladium acetate.
• acids with a pKa of less than 4 are mineral acids such as perchloric acid, sulphuric acid, phosphoric acid and nitrous acid, sulphonic acids such as 2-hydroxypropane-2-sulphonic acid, para-toluene sulphonic acid, methane sulphonic acid and trifluoromethane sulphonic acid and carboxylic acids such as trifluoroacetic acid, trichloroacetic acid, dichloroacetic acid, difluoroacetic acid, tartaric acid and 2,5-dihydroxybenzoic acid.
• mineral acids such as perchloric acid, sulphuric acid, phosphoric acid and nitrous acid
• sulphonic acids such as 2-hydroxypropane-2-sulphonic acid, para-toluene sulphonic acid, methane sulphonic acid and trifluoromethane sulphonic acid
• carboxylic acids such as trifluoroacetic acid, trichloroacetic acid,
• the catalyst composition contains as component b) an anion of an acid with a pKa of less than 2 and in particular an anion of a sulphonic acid such as para-toluene sulphonic acid or an anion of a carboxylic acid such as trifluoroacetic acid.
• Component b) is preferably present in the catalyst compositions in a quantity of 0.5 to 200 and in particular 1.0 to 100 equivalents per gat palladium.
• Component b) may be incorporated in the catalyst compositions in the form of an acid or in the form of a salt. Possible salts are non-noble transition metal salts.
• component b) is applied as a salt of a non-noble transition metal, preference is given to a copper, especially a cupric salt. If desired, components a) and b) can be combined in a single compound. An example of such a compound is palladium para-tosylate.
• Component c) is preferably present in the catalyst compositions in a quantity of 0.5-200 and in particular 1-50 moles per mol palladium compound.
• Bridging groups X and Y in component c) are linked to each other via the two carbon atoms shown in the general formula. Besides these bonds, there may also be an additional bond between bridging groups X and Y such as in 1,10-phenantroline and compounds derived therefrom. If besides carbon atoms, bridging groups X and Y also contain other atoms, these atoms are preferably nitrogen atoms. There is also preference for components c) in which bridge groups X and Y are the same.
• suitable components c) are 2,2′-bipyridine and compounds derived therefrom, such as 4,4′-dimethyl-2,2′-bipyridine, 4,4′-dichloro-2,2′-bipyridine, 4,4′-dimethoxy-2,2′-bipyridine,and 4,4′-dicarboxy-2,2′-bipyridine.
• suitable components c) are 1,10-phenantroline and compounds derived therefrom, such as 5-chloro-1,10-phenantroline, 4,7-diphenyl-1,10-phenantroline, 4,7-dimethyl-1,10-phenantroline, 2,9-dichloro-1,10-phenantroline, 1,10-phenantroline-5-sulphonic acid and 4,7-diphenyl-1,10-phenantroline disulphonic acids.
• Examples of other suitable components c) are 2,2′-biquinoline, 2-(2-pyridyl) benzimidazole and 3-(2-pyridyl)-5,6-diphenyl-1,2,4-triazine.
• An optionally substituted 2,2′-bipyridine or an optionally substituted 1,10-phenantroline is preferred as component c).
• 2,2′-bipyridine and 1,10-phenantroline are particularly preferred.
• An organic oxidizing agent is suitably included in the catalyst compositions as component d).
• organic oxidizing agents which can be used as component d) in the catalyst compositions are 1,2- and 1,4-quinones, aliphatic nitrites such as methyl nitrite, ethyl nitrite, propyl nitrite and butyl nitrite, aromatic nitro compounds such as nitrobenzene, nitrotoluene and nitrochlorobenzene and peroxides such as di-tert.butyl peroxide and dicumyl peroxide.
• Quinones are preferred, and in particular 1,4-quinones.
• other quinones such as optionally substituted naphthoquinones and anthraquinones may also be used.
• 1,4-benzoquinone or 1,4-naphthoquinone is used as component d).
• the quantity of organic oxidizing agent used is preferably 1-10000 and in particular 10-5000 moles per gat palladium.
• the preparation of the polymers according to the invention is preferably carried out by contacting the monomers with a solution of the catalyst composition in a diluent in which the polymers are almost or entirely insoluble. During the polymerization the polymers are obtained in the form of a suspension in the diluent. Examples of suitable diluents are lower alcohols such as methanol and ethanol.
• suitable diluents are lower alcohols such as methanol and ethanol.
• the polymerization can take place either batchwise or continuously. If desired, the polymerization can also be carried out in the gas phase.
• the quantity of catalyst composition used in the preparation of the polymers can vary within wide limits.
• a quantity of catalyst is used which preferably contains 10 ⁇ 7-10 ⁇ 3 and in particular 10 ⁇ 6-10 ⁇ 4 gat palladium.
• the preparation of the polymers is preferably carried out at a temperature of 20-200°C and a pressure of 1-200 bar and in particular at a temperature of 30-150°C and a pressure of 20-100 bar.
• the molar ratio of the olefinically unsaturated compounds relative to carbon monoxide in the mixture to be polymerized is preferably 10:1-1:5 and in particular 5:1-1:2.
• the carbon monoxide used in the preparation of the polymers according to the invention does not need to be pure. It may contain impurities such as hydrogen, carbon dioxide and nitrogen.
• a carbon monoxide/ethylene/butene-1 terpolymer was prepared as follows. 180 ml Methanol and 20 ml liquefied butene-1 were introduced into a mechanically stirred autoclave with a volume of 300 ml. After the contents of the autoclave had been heated to 85°C, a 1:1 carbon monoxide/ethylene mixture was forced into it until a pressure of 55 bar was reached. Subsequently, a catalyst solution was introduced into the autoclave consisting of 6 ml methanol, 0.01 mmol palladium acetate, 0.2 mmol trifluoroacetic acid, and 0.01 mmol 1,3-bis(diphenylphosphino)propane.
• the pressure was maintained at 55 bar by forcing in a 1:1 carbon monoxide/ethylene mixture. After 5 hours the polymerization was ended by cooling to room temperature and releasing the pressure. The polymer was filtered off, washed with methanol and dried at 70°C.
• a carbon monoxide/ethylene/dodecene-1 terpolymer was prepared in virtually the same manner as the terpolymer in example 1, but with the following differences:
• a carbon monoxide/ethylene/methyl acrylate terpolymer was prepared as follows. Into a stirred autoclave with a volume of 250 ml was introduced a catalyst solution consisting of 40 ml methanol, 0.1 mmol palladium acetate, 2 mmol cupric para-tosylate and 0.15 mmol 1,3-bis(diphenylphosphino)propane.
• a carbon monoxide/ethylene/methyl ester of 10-undecenoic acid was prepared in virtually the same manner as the terpolymer in example 3, but with the following differences:
• a carbon monoxide/ethylene/10-undecenoic acid terpolymer was prepared in virtually the same manner as the terpolymer in example 3, but with the following differences:
• a carbon monoxide/ethylene/maleic acid anhydride terpolymer was prepared in virtually the same manner as the terpolymer in example 3, but with the following differences:
• a carbon monoxide/ethylene/maleic acid anhydride terpolymer was prepared in a virtually analogous manner as the terpolymer in example 3, but with the following differences:
• a carbon monoxide/ethylene/butene-2 terpolymer was prepared in virtually the same manner as the terpolymer in example 3, but with the following differences:
• a carbon monoxide/ethylene/butene-2 terpolymer was prepared in virtually the same manner as the terpolymer in example 3, but with the following differences:
• examples 7 and 9 are according to the invention.
• terpolymers of carbon monoxide with ethylene and with a third monomer E maleic acid anhydride or butene-2
• component c catalyst compositions containing 2,2′-bipyridine as component c
• Examples 1-6 and 8 fall outside the scope of the invention, and are included for the purpose of comparison.
• terpolymers of carbon monoxide with ethylene and with a third monomer A butene-1 or dodecene-1
• B methyl acrylate, 10-undecenoic acid or the methyl ester of 10-undecenoic acid
• E maleic acid anhydride or butene-2
• catalyst compositions containing 1,3-bis(diphenylphosphino)propane as component c.
• Examples 1 and 2 demonstrate the suitability of diphosphine containing catalyst compositions for the preparation of terpolymers of carbon monoxide with ethylene and with a mono-olefin (A) with terminal double bond.
• Examples 3-5 demonstrate the suitability of diphosphine containing catalyst compositions for the preparation of terpolymers of carbon monoxide with ethylene and with a mono-olefin (B) in which a carboxylate group is present and with a terminal double bond.
• terpolymers of carbon monoxide with ethylene and with a third monomer E were prepared in the presence of catalyst compositions containing a diphosphine as component c), these terpolymers contained on average more than 2000 -(CO)-(C2H4)- units per -(CO)-E′- unit.

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• 1988
  • 1988-10-17 CA CA000580360A patent/CA1329858C/en not_active Expired - Fee Related
  • 1988-11-02 DE DE3851410T patent/DE3851410T2/de not_active Expired - Fee Related
  • 1988-11-02 EP EP88202448A patent/EP0315279B1/de not_active Expired - Lifetime
  • 1988-11-02 AU AU24622/88A patent/AU607273B2/en not_active Ceased
  • 1988-11-02 JP JP63278484A patent/JP2706108B2/ja not_active Expired - Lifetime
  • 1988-11-04 US US07/267,142 patent/US4921937A/en not_active Expired - Lifetime

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